Inkjet ink composition containing anti-kogation agents

ABSTRACT

Ink compositions and methods of using the same are disclosed. An example ink composition includes an inkjet vehicle, from about 0.1 wt % to about 10 wt % of colorants, from about 0.01 wt % to about 10 wt % of anti-kogation agents, and from about 0.01 wt % to about 10 wt % of dispersed resin beads.

BACKGROUND

The use of inkjet printing systems has grown dramatically in recent years, which is attributed to substantial improvements in print resolution and overall print quality coupled with appreciable reduction in cost. Notwithstanding their recent success, intensive research and development efforts continue toward improving inkjet print quality, while further lowering cost to the consumer.

With inkjet printing, a desired printed image is formed when a precise pattern of dots is ejected from a drop-generating device, known as a printhead, onto a print medium. The printhead has an array of precisely formed nozzles located on a nozzle plate and attached to an inkjet printhead substrate. The inkjet printhead substrate incorporates an array of firing chambers that receive inkjet ink through fluid communication with one or more ink reservoirs. Each firing chamber has a resistor element, known as a firing resistor, located opposite the nozzle so that the inkjet ink collects between the firing resistor and the nozzle. Each resistor element is typically a pad of a resistive material and measures about 35 μm×35 μm. The printhead is held and protected by an outer packaging referred to as a print cartridge or an inkjet pen. Upon energizing of a particular resistor element, a droplet of inkjet ink is expelled through the nozzle toward the print medium. The firing of ink droplets is typically under the control of a microprocessor, the signals of which are conveyed by electrical traces to the resistor elements, forming alphanumeric and other characters on the print medium. The small scales of the nozzles, which are typically 10 μm to 40 μm in diameter, require that the ink does not clog the nozzles. However, repeated firings of the resistor elements, which are designed to withstand millions of firings over the life of the print cartridge, result in fouling of the resistor elements with residue and degradation of pen performance. This build up of residue is known as kogation. The term “kogation” is, thus, used herein to refer to the buildup of the residue, or koga, on a surface of the resistor element in the inkjet pen.

To produce high quality images, the inkjet ink has to be compatible with the inkjet pen and the print medium. In addition, the ink has to be capable of passing through the inkjet orifice without clogging the orifice plate.

Inkjet ink typically includes one or more colorants dissolved or dispersed in an aqueous-based ink vehicle and can also contain anti-kogation components. Such anti-kogation components have been used to counter the kogation effect. However, such components tend to be not stable in the ink composition and often precipitate. Such precipitation phenomenon results in a deposition phenomenon which tend clog the nozzle of the print head

Clogging of ink occurs when ink drops, exiting the orifices, leave behind minute amounts of ink on the orifice plate around each orifice. The inkjet ink collects on an outer surface of the orifice plate or puddles adjacent to the edge of the orifice. Such clogging happens at the fore end of the narrow nozzle so that the direction and quantity of ink jetted become unstable. This clogging effect results in that the size and the speed of ink drops vary exceedingly whereby it becomes impossible to obtain a clear record and jet printing is hampered. This phenomena result thus in poor printing performances.

Clogging naturally happen on inks, however, this phenomenon is accentuated by precipitation of some components of ink composition, such as anti-kogation components, and furthermore, is accentuated when metal ions contaminate ink composition.

It has thus often created challenges to formulate ink compositions which do not have a kogation effect and which do not result in clogging the nozzle of the printing machine; in other words, which can be effectively used with inkjet printing techniques and which provide good image printing performances.

BRIEF DESCRIPTION OF THE DRAWINGS

In order to better understand the present disclosure, some embodiments will be described below by way of non-limiting examples only, with reference to figures, wherein:

FIG. 1 is a graph representing drop weight (ng) versus million drops/nozzle (MDPN) of a control ink composition compared to an ink composition according to embodiment(s) of the present disclosure; and

FIG. 2 depicts 100× optical images of resistor surfaces after kogation testing on a resistor life tester for a control ink composition and an ink composition according to embodiment(s) of the present disclosure.

DETAILED DESCRIPTION

Embodiments of the present disclosure will employ, unless otherwise indicated, techniques of synthetic organic chemistry, ink chemistry, media chemistry, printing chemistry, and the like, that are within the skill of the art. Such techniques are explained fully in the literature. The following examples are put forth to provide those of ordinary skill in the art with a complete disclosure and description of how to perform the methods and use the compositions disclosed and claimed herein. Efforts have been made to ensure accuracy with respect to numbers (e.g., amounts, temperature, etc.) but some errors and deviations should be accounted for. Unless indicated otherwise, temperature is in ° C., and pressure is at or near atmospheric. Standard temperature and pressure are defined as 20° C. and 1 atmosphere. Unless indicated otherwise, the viscosity is expressed in cP and is measured at a temperature of 25° C.

Before embodiments of the present disclosure are described in detail, it is to be understood that, unless otherwise indicated, the present disclosure is not limited to particular materials, and processes disclosed herein as such may vary to some degree. It is also to be understood that the terminology used herein is for purposes of describing particular embodiments only, and is not intended to be limiting, as the scope of the present invention will be defined only by the appended claims and equivalents thereof.

In the present specification, and in the appended claims, the following terminology will be used: the singular forms “a”, “an”, and “the” include plural referents unless the context clearly dictates otherwise. Thus, for example, reference to “a support” includes a plurality of supports. The terms “about” and “approximately,” when referring to a numerical value or range is intended to encompass the values resulting from experimental error that can occur when taking measurements. Concentrations, amounts, and other numerical data may be presented herein in a range format. It is to be understood that such range format is used merely for convenience and brevity and should be interpreted flexibly to include not only the numerical values explicitly recited as the limits of the range, but also to include all the individual numerical values or sub-ranges encompassed within that range as if each numerical value and sub-range is explicitly recited. For example, a weight range of about 1 weight percentage (wt %) to about 20 weight percentage (wt %) should be interpreted to include not only the explicitly recited concentration limits of 1 wt % to approximately 20 wt %, but also to include individual concentrations such as 2 wt %, 3 wt %, 4 wt %, and sub-ranges such as 5 wt % to 15 wt %, 10 wt % to 20 wt %, etc.

As used herein, “images” refers to marks, signs, symbols, figures, indications, and/or appearances deposited upon a material or substrate with either visible or an invisible ink composition. Examples of an image can include characters, words, numbers, alpha-numeric symbols, punctuation, text, lines, underlines, highlights, and the like.

In some embodiments, the inkjet ink composition includes an inkjet vehicle, from about 0.1 to about 10 weight percentage of colorants, from about 0.01 to about 10 weight percentage of anti-kogation agents and from about 0.01 to about 10 weight percentage of a dispersed resin beads.

In some embodiments, the ink composition is an inkjet ink printing composition. By inkjet composition, it is meant herein that the composition is very well adapted to be used in an inkjet device and in an inkjet printing process. In other words, the ink composition is suitable for inkjet ink printing.

It has likewise been observed that ink compositions often tend to suffer from kogation of resistors, resulting in shortened lifetime of the printhead and decreased print quality at earlier stages in the life of the printhead. Anti-kogation elements have often been used to avoid such kogation problems. However, inks containing such anti-kogation elements tend to suffer from clogging problems. Indeed, without being linked by any theory, it is believed that the anti-kogation elements react with metal ions, and create insoluble salts that precipitate and load the filters present in the printhead, and ultimately clog the flow of ink to the nozzles.

In some embodiments, inkjet ink composition of the present disclosure reduces the clogging phenomenon that can happen in internal ink channels, in firing chambers, or in nozzles of the printhead. The composition of the present disclosure has a good affect on the filterability of the ink (i.e., the ink can be easily filtered). This property reflects the anti-clogging effect of the ink composition. Small-mesh filters are used in the ink circulation system for preventing the above mentioned clogging at the narrow nozzle portion. However, this design encounters problem that the filters clog. Thus, by reducing the clogging effect, the composition of the present disclosure enhances therefore the filterability of the ink composition. Thus, in some embodiments, the composition offers a means to avoid filterability issues and/or potential nozzle clogging issues.

In some embodiments, the presence of anti-kogation agents and water soluble components, such as disclosed herein, reduces the amount of multivalent metal ion (such as calcium) presents in ink composition. Without being bound by any theory, it is believed that the efficiency of components to bind calcium reflects the anti-clogging effect and the filterability characteristics of ink compositions.

In addition, the composition of the present disclosure presents improved printing characteristics. Indeed, kogation and clogging problems tend to reduce drop velocity and drop weight and tend to reduce the efficiency of drop ejection. A loss of drop weight over the life of the inkjet pen reduces the color saturation or optical density of the inkjet ink on the print medium and, therefore, degrades print quality. Furthermore, a loss of drop weight over the life of the inkjet pen reduces the accuracy of drop placement on the print medium and, therefore, degrades print quality. Thus, by reducing the kogation and clogging phenomenon, the composition disclosed herein has improved printing characteristics. Thus, as examples, the ink composition improves drop velocity, and as other examples, improves efficiency of drop ejection.

In some embodiments, the present disclosure relates to method of prolonging the service life of an inkjet print head, to be used for an inkjet recording method, including discharging ink from an orifice wherein the ink contains: an inkjet vehicle, from about 0.1 to about 10 weight percentage of colorants, from about 0.01 to about 10 weight percentage of anti-kogation agents and from about 0.01 to about 10 weight percentage of resin beads.

In some embodiments, the pH of the ink composition may be varied as desired. In some embodiments, the pH of the ink ranges from about 3 to about 11, depending upon the type of colorant being used. In an example, the pH of the present ink is from about 5 to about 9 and, in another example, from about 5.5 to about 7.5. The pH of the ink compositions may be adjusted by the addition of organic or inorganic acids or bases, i.e., pH adjusting agent. Typical pH adjusting agent includes inorganic acids such as hydrochloric, phosphoric and sulfuric acids. Typical organic acids include methane sulfonic, acetic and lactic acids. Typical inorganic bases include alkali metal hydroxides and carbonates. In some embodiments, pH adjusting agent is ammonium hydroxide. Any suitable amount of the pH adjusting agent can be used. In an example, the pH adjusting agent is used in an amount of from about 0.1 to about 1 percentage by weight, and, in another example, in an amount of from about 0.3 to about 0.7 percentage by weight of the composition.

In some embodiments, the ink compositions have a viscosity within the range of about 1.0 to about 10 cps, and, in other embodiments, of about 1.0 to about 7.0 cps, as measured at 25° C., in order to achieve the desired rheological characteristics. As indicated above, the viscosity of the ink composition is conveniently regulated, as known to those of ordinary skill in the art, for instance, by suitable choice of the quantity and the molecular weight of the binders resin, the organic solvent, the wax, and other agents.

In some embodiments, the ink composition includes resin beads. In an example, the resin beads are dispersed into the liquid vehicle of the ink composition.

In some embodiments, the resin beads are present in an amount representing from about 0.01 to about 10 weight percentage. In some other examples, the resin beads are present in an amount representing from about 0.10 to about 10 weight percentage by total weight of the ink composition and, in other examples, in an amount representing from about 0.20 to about 2 weight percentage by total weight of the ink composition

During the inkjet process, due to their specific size, the beads will stay on the printhead, meaning thus that they are not going to be ejected via the nozzle and they will not be ejected onto the substrate. As an example, the beads would stay behind filter in the ink supply or in pen body or in the ink supply container. In some examples, the ink flows through the filter to the firing chamber whereas the beads, having a size unable to pass through the filter, stay behind.

Thus, in some embodiments, the size of the beads is bigger than the pore size of the filter present in the pen's ink delivery system. Thus, in some embodiments, the beads have a size of at least 1 μm in diameter. In other embodiments, the resin beads have a size ranging from about 5 to about 800 μm in diameter; in some other embodiments, the resin beads have a size ranging from about 50 to about 600 μm in diameter. In yet other embodiments, the resin beads have a size ranging from about 450 to about 550 μm in diameter.

As used herein, the term beads refers to any spherical or irregular shaped particles that are dispersed in the ink composition and that have the capacity of interfering and trapping ion materials. As an example, the beads are water dispersible. In some embodiments, the beads are ion-exchange resins and have the capacity of interfering and trapping ionic materials, and especially, multivalent metal ion materials.

In some embodiments, the resin beads include an organic or an inorganic polymer and a functional group. In some examples, the resin beads contains, as a functional group, any groups that would bind multivalent metal ions. Thus, in some embodiments, the resin beads are ion-exchange resin beads.

In some embodiments, the functional group can be any entity including a di-acid groups, or any homologues of ethylenediamine with acetic acid or any substituted methylphosphonic acid. In some other embodiments, resin beads contain, as functional group, a compound selected from the group consisting of iminodiacetic acid and imino-diacetate.

In some other embodiments, resin beads contain a functional group selected from the group consisting of iminodiacetic acid group (IDA) or aminomethylphosphonic acid (AMPA) group or diethylenetriaminetetraacetate (TAAcOH) group.

In some embodiments, the resins are organic polymers or inorganic polymers. As an example, the resins are based on cross-linked polystyrene. In some embodiments, the resins encompass high molecular composition-made matrixes. Such high molecular composition-made matrixes are of the phenol type, styrene type, acryl type, acrylic acid-type and pyridine-type. In some other embodiments, the resins are synthetic resins such as: polyamide, unsaturated polyester, polyurethane, epoxy, silicone or copolymer of an unsatured dicarboxylic acid and styrene. As an example, the resins containing the functional group are polystyrene cross-linked with divinylbenzene.

In some other examples, the polymer, constituting the resin, is an inorganic polymer such as precipitated silica. As another example, the resin beads are precipitated silica with triamine-tetra-acetic acid surface modification or salt thereof.

Examples of resin beads include, but are not limited to, beads that are commercially available under the tradename QuadraPure® (available from Reaxa Corp.) or under the tradename SiliaBond® (available from Silicycle Inc.).

In some embodiments, the inkjet ink composition includes anti-kogation agents. As anti-kogation agent, it is meant herein any components that prevent or reduce the kogation effect. The anti-kogation agent used in the ink composition may be an anionic surfactant, a nonionic surfactant, a zwitterionic surfactant, an amphoteric surfactant, or mixtures thereof.

As used herein, the term “amphoteric surfactant” refers to a surfactant that includes both cationic groups and anionic groups. If the amphoteric surfactant is present in an acidic environment, the amphoteric surfactant has cationic groups, while the amphoteric surfactant has anionic groups in a basic environment. At isoelectric point (IEP), the amphoteric surfactant has an overall neutral charge because both cationic groups and anionic groups are present.

As used herein, the term “zwitterionic surfactant” refers to a surfactant that includes both anionic groups and cationic groups and, therefore, has a neutral charge. The zwitterionic surfactant differs from the amphoteric surfactant in that the charge on the zwitterionic surfactant is not as sensitive to changes in pH.

In some embodiments, the anti-kogation agent is an anionic surfactant. In other embodiments, the anti-kogation agent has a neutral charge. As such, the anti-kogation agent may be nonionic, amphoteric, or zwitterionic. In some embodiments, the ink composition has a neutral pH so that the anti-kogation agent has an overall neutral charge. In some embodiments, the anti-kogation agent is a phosphate-containing surfactant, such as a phosphate ester surfactant. Examples of phosphate ester surfactants include, but are not limited to, surfactants that are commercially available under the tradename Emphos®, DeSophoS®, Hostaphat®, ESI-Terge®, Emulgen®, Crodafos®, Dephotrope®, and DePhOS®, which are available from Witco Corp. (Middlebury, Conn.), Clariant GmbH (Frankfurt, Germany), Cook Composites and Polymers Co., (Kansas City, Mo.), Kao Specialties Americas LLC (High Point, Nalco), Croda Inc. (Parsippany, N.J.), DeForest Enterprises, Inc. (Boca Raton, Fla.), and DeForest Enterprises, Inc. (Boca Raton, Fla.), respectively. Specific examples of phosphate ester surfactants that may be used include, but are not limited to, Crodafos®N-3 Acid, Emphos®9NP, Emphos®CS121, Emphos®CS131, Emphos®CS141, Emphos®CS1361, Hostaphat®LPKN, ESI-Terge®320, ESI-Terge®330, DePhoS®8028, Emulgen®BL-2PK, DeSophos®4P, DeSophoS®6 MPNa, DeSophoS®8DNP, DeSophoS®9NP, DeSophoS®30NP or Dephotrope®CAS-MF. In addition, mixtures of these phosphate ester surfactants may be used.

In some embodiments of the present disclosure, the inkjet ink composition includes a phosphate-containing surfactant as anti-kogation agent. In some other embodiments, the anti-kogation agent is a phosphate ester surfactant. In yet some other embodiments, the anti-kogation agent is a phosphate ester of a fatty alcohol alkoxylate surfactant. In some embodiments, the phosphate ester of a fatty alcohol alkoxylate is a mixture of mono- and di-esters. In other embodiments, the phosphate ester of a fatty alcohol alkoxylate has an acid number ranging from 50 to 150. In some embodiments, the anti-kogation agent is an ethoxylated mono-oleyl phosphate ester.

The anti-kogation agent may be oleth-3 phosphate, a nonylphenol ethoxylate phosphate ester, a salt of a nonylphenol ethoxylate phosphate ester, an organo-phosphate, an aliphatic phosphate ester, a phosphated nonylphenoxy polyethoxy ethanol, or a salt of ethyl-hexanol ethoxylated phosphate ester (2EH-2EO). In other embodiments, the anti-kogation agent is selected from the group consisting of oleth-3 phosphate, oleth-10 phosphate, oleth-5 phosphate, dioleyl phosphate, ppg-5-ceteth-10 phosphate, C₉-C₁₅ alkyl monophosphate, deceth-4 phosphate, and mixtures thereof.

In other embodiments, the inkjet ink composition includes, as anti-kogation agent, a compound having the formula (II) below, wherein n is from 0 to 15.

Examples of anti-kogation agent include surfactants of the Crodafos®family available from Croda Inc such as Crodafos®N3A, Crodafos®N3E, Crodafos®N10A, Crodafos®HCE and Crodafos®SG. Other examples of the phosphate-containing surfactants include Arlatone®Map 950 available from Croda Inc; Monofax® 831, Monofax®1214 available from Mona Industries; Monalube® 215 and Atlox®DP13/6 available from Croda Inc.

In some embodiments, the anti-kogation agent is present in an amount representing from about 0.01 to about 10 percentage by weight (wt %) of total weight of the ink composition. In some examples, the anti-kogation agent is present in an amount representing from about 0.2 to about 3 weight percentage. In other examples, the anti-kogation agent is present in an amount representing from about 0.4 to about 1 weight percentage of the total weight of the ink composition.

The ink composition includes one or more colorants that impart the desired color to the printed message. As used herein, “colorant” includes dyes, pigments, and/or other particulates that may be suspended or dissolved in an ink vehicle.

The colorant system is present in an amount representing from about 0.1 to about 10 percentage by weight (wt %), in some examples, in an amount representing from about 1 to about 6 percentage by weight, and in other examples, in an amount representing from about 1 to about 4 percentage by weight of the ink composition. The colorant is generally present in an amount required to produce the desired contrast and readability.

In some embodiments, according to the present disclosure, the ink includes pigments as colorants. As used herein, “pigment” refers to a colorant particle that is substantially insoluble in the liquid vehicle in which it is used. Pigments can be dispersed using a separate dispersing agent, or can be self-dispersed, having a dispersing agent attached to the surface of the pigment.

As used herein, “self-dispersed” generally refers to pigments that have been functionalized with a dispersing agent, such as by chemical attachment of the dispersing agent to the surface of the pigment. The dispersing agent can be a small molecule or a polymer or oligomer. The dispersing agent can be attached to such pigments to terminate the outer shell of the pigment with a charge, thereby creating a repulsive nature that reduces agglomeration of pigment particles within the liquid vehicle. Another way to disperse carbon black is to surface treat the carbon (with ozone, as an example) to create charged functional groups on the surface of the carbon itself.

The pigments that can be used in accordance with embodiments of the present disclosure include both self-dispersed pigments as well as dispersed pigments, e.g., pigments dispersed by a separate dispersing agent that is not covalently attached to the surface. If self-dispersed, a dispersant is typically prepared in a precursor form, and then the precursor is attached to the pigment to chemically modify the surface of the pigment. In some embodiments, the dispersant can be attached to the pigment using various precursor materials, such as para-aminobenzoic acids, isophthalic acids, tricarboxylic acids, carboxylic groups, sulfonylic groups, phosphates, oligomers, polymers, and isomers thereof, for example.

As alluded to, pigment colorant can be used in accordance with embodiments of the present disclosure. Specifically, if black is used, the black pigment can be any commercially available black pigment that provides acceptable optical density and print characteristics. Such black pigments can be manufactured by a variety of known methods such as channel methods, contact methods, furnace methods, acetylene methods, or thermal methods, and are commercially available from such vendors as Cabot Corporation, Columbian Chemicals Company, Evonik, Mitsubishi, and E.I. DuPont de Nemours and Company. For example, commercially available carbon black pigments include Color Black FW 200, Color Black FW 2V, Color Black FW1, Color Black FW 18, Color Black FW S160, Color Black FW S170, Printex including 95, 85, 75, 55, 45, 300, 35, 25, 200, 12, and Special Blacks including, 4A, 4, 5, 6, 550, 350, 250; BP1100, BP900, BP800, M1100, M900, M800, Monarch 1400, Monarch 1300, Monarch 1000, Monarch 900, Monarch 880, and Monarch 700; Cab-O-Jet 200 and Cab-O-Jet 300; Raven 2500ultra, Raven 2000, Raven 7000, Raven 5750, Raven 5250, Raven 5000, and Raven 3500; 45 B, and combinations thereof.

In addition to black, other pigment colorants can be used, such as cyan, magenta, yellow, blue, orange, green, pink, etc. Suitable organic pigments include, for example, azo pigments including diazo pigments and monoazo pigments, polycyclic pigments (e.g., phthalocyanine pigments such as phthalocyanine blues and phthalocyanine greens, perylene pigments, perynone pigments, anthraquinone pigments, quinacridone pigments, dioxazine pigments, thioindigo pigments, isoindolinone pigments, pyranthrone pigments, and quinophthalone pigments), insoluble dye chelates (e.g., basic dye type chelates and acidic dye type chelate), nitropigments, nitroso pigments, anthanthrone pigments such as PR168, and the like. Representative examples of phthalocyanine blues and greens include copper phthalocyanine blue, copper phthalocyanine green and derivatives thereof (Pigment Blue 15 and Pigment Green 36). Representative examples of quinacridones include Pigment Orange 48, Pigment Orange 49, Pigment Red 122, Pigment Red 192, Pigment Red 202, Pigment Red 206, Pigment Red 209, Pigment Violet 19 and Pigment Violet 42. Representative examples of anthraquinones include Pigment Red 43, Pigment Red 194, Pigment Red 177, Pigment Red 216 and Pigment Red 226. Representative examples of perylenes include Pigment Red 123, Pigment Red 190, Pigment Red 189 and Pigment Red 224. Representative examples of thioindigoids include Pigment Red 86, Pigment Red 87, Pigment Red 198, Pigment Violet 36, and Pigment Violet 38. Representative examples of heterocyclic yellows include Pigment Yellow 1, Pigment Yellow 12, Pigment Yellow 13, Pigment Yellow 14, Pigment Yellow 17, Pigment Yellow 73, Pigment Yellow 90, Pigment Yellow 110, Pigment Yellow 117, Pigment Yellow 120, Pigment Yellow 128, Pigment Yellow 138, Pigment Yellow 150, Pigment Yellow 151, Pigment Yellow 155, and Pigment Yellow 213. Such pigments are commercially available in powder, press cake, or dispersion form from a number of sources.

The pigments of the present disclosure can be from about 5 nm to about 10 μm in size; in another example, the pigments can be from 10 nm to about 500 nm in size, although sizes outside this range can be used if the pigment can remain dispersed and provide adequate printing properties.

In some embodiments, the inks can include dyes as colorants. Examples of dyes suitable for use in the preparation of the ink composition include, but are not limited to, the yellow dyes such as C.I. Yellow 19 (C.I. 13900A), C.I. Yellow 21 (C.I. 18690), C.I. Yellow 61, C.I. Yellow 80, FD&C Yellow #5, and the like, the orange dyes such as C.I. Orange 1 (C.I. 11920), C.I. Orange 37, and the like, red dyes such as C.I. Solvent Red 8, C.I. Red 81, C.I. Solvent Red 82, and the like, pink dyes such as Diaresin Pink M (Mitsubishi Chemical Industries, Ltd.), and the like, violet dyes such as C.I. Solvent Violet 8, and the like, blue dyes such as C.I. Solvent Blue 2, C.I. Solvent Blue 11, and the like, black dyes such as C.I. Solvent Black 3, Acid Black 123, and the like. Some of the pigments and dyes are commercially available in convenient dispersions and may be used in the preparation of the ink composition according to embodiments of the present disclosure. In some embodiments, the ink includes a mixture of dyes and pigments as colorants.

As used herein, “liquid vehicle” is defined to include any liquid composition that is used to carry colorants, including pigments, to a substrate. A wide variety of liquid vehicle components may be used in accordance with embodiments of the present disclosure. Such liquid vehicle may include a mixture of a variety of different agents, including without limitation, other surfactants, solvent and co-solvents, buffers, biocides, viscosity modifiers and water. In some embodiments, the liquid vehicle is an inkjet liquid vehicle.

In some embodiments, organic solvents are part of the liquid vehicles. Organic solvents are typically used to increase the solubility or the dispersibility of the resin or of the colorant that might be present in the composition. Any suitable organic solvent can be used. Examples of suitable classes of organic solvents include the polar solvents such as amides, esters, ketones, lactones and ethers. Examples of suitable organic solvents include N-methylpyrrolidone (NMP), dimethyl sulfoxide, sulfolane, and glycol ethers. In some embodiments, the solvent is 2-pyrrolidone or a derivative of 2-pyrrolidone, such as 1-(2 hydroxyethyl)-2-pyrrolidone. In some other embodiments, the liquid vehicle includes a plurality of solvents.

As an example, the solvent is used in an amount representing from about 0.1 to about 30 weight percentage of the ink composition and; in other embodiments, in an amount of from about 8 to about 25 weight percentage of the ink composition.

In some embodiments, the ink composition includes water. In some embodiments, water is used as the ink carrier for the composition and is part of the liquid vehicle. Generally, the water makes up the balance of the ink composition, and may be present in an amount representing from about 40 to about 90 weight percentage, in some embodiments representing from about 50 to about 80 weight percentage by weight of the total composition. In order to prevent the clogging of inkjet tip by dissolved salts in the water, deionized water may be used in the preparation of the ink composition.

In addition to water, various types of agents may be employed in the ink composition to optimize the properties of the ink composition for specific applications. For example, the ink composition may also include any number of buffering agents and/or biocides. Any number of commonly known buffers may be used to establish a desired pH level in the ink system. Additionally, in some embodiments, various biocides are used to inhibit growth of undesirable microorganisms. Several examples of suitable biocides include, but are in no way limited to, benzoate salts, sorbate salts, commercial products such as Nuosept® (ISP), Ucarcide® (Dow), Vancide® (RT Vanderbilt Co.), and Proxel® (Avecia), Kordek® MLX (Rohm and Haas) and other known biocides. Such biocides may be comprised in amount representing less than about 5 weight percentage of the ink composition. In some examples, biocides represents from about 0.05 to about 2 weight percentage of the ink composition.

In further detail with respect to the surfactant, the inkjet ink compositions can be substantially free of surfactant other than the phosphate-containing surfactant of the anti-kogation agent. However, certain second surfactants can also be used and may include standard water-soluble surfactants such as alkyl polyethylene oxides, alkyl phenyl polyethylene oxides, polyethylene oxide (PEO) block copolymers, acetylenic PEO, PEO esters, PEO amines, PEO amides, dimethicone copolyols, ethoxylated surfactants, fluorosurfactants, and mixtures thereof. In one example, a fluorosurfactant can be used as the second surfactant. In other examples, a secondary alcohol ethoxylated surfactant can be used. If used, the second surfactant can be present at from about 0.001 to about 10 weight percentage, and, in other examples, can be present at from about 0.001 to about 0.1 weight percentage of the inkjet ink composition.

In some embodiments, the ink composition can contain latexes. Latexes include both latex particulates as well as the aqueous medium in which the latex particulates are dispersed. Latex is a liquid suspension including a liquid (such as water and/or other liquids) and polymeric particulates from about 20 nm to about 500 nm in size. As an example, the polymeric particulate can be present in the liquid at from about 0.5 to about 20 weight percentage. Such polymeric particulates can include a plurality of monomers that are typically randomly polymerized, and can be crosslinked.

Any latex polymer commercially available can be used in the inks of the present disclosure including self-dispersed and functionalized latex polymers. Latex polymers can be prepared using any of a number of known emulsion polymerization techniques where co-monomers are dispersed and polymerized in a discontinuous phase of an emulsion. Monomers that are often used include ethyl acrylate; ethyl methacrylate; benzyl acrylate; benzyl methacrylate; propyl acrylate; propyl methacrylate; iso-propyl acrylate; iso-propyl methacrylate; butyl acrylate; butyl methacrylate; hexyl acrylate; hexyl methacrylate; octadecyl methacrylate; octadecyl acrylate; lauryl methacrylate; lauryl acrylate; hydroxyethyl acrylate; hydroxyethyl methacrylate; hydroxyhexyl acrylate; hydroxyhexyl methacrylate; hydroxyoctadecyl acrylate; hydroxyoctadecyl methacrylate; hydroxylauryl methacrylate; hydroxylauryl acrylate; phenethyl acrylate; phenethyl methacrylate; 6-phenylhexyl acrylate; 6-phenylhexyl methacrylate; phenyllauryl acrylate; phenyllauryl methacrylate; 3-nitrophenyl-6-hexyl methacrylate; 3-nitrophenyl-18-octadecyl acrylate; ethyleneglycol dicyclopentyl ether acrylate; vinyl ethyl ketone; vinyl propyl ketone; vinyl hexyl ketone; vinyl octyl ketone; vinyl butyl ketone; cyclohexyl acrylate; methoxysilane; acryloxypropyhiethyl-dimethoxysilane; trifluoromethyl styrene; trifluoromethyl acrylate; trifluoromethyl methacrylate; tetrafluoropropyl acrylate; tetrafluoropropyl methacrylate; heptafluorobutyl methacrylate; iso-butyl acrylate; iso-butyl methacrylate; 2-ethylhexyl acrylate; 2-ethylhexyl methacrylate; iso-octyl acrylate; and iso-octyl methacrylate.

As an example, the ink composition of the present disclosure can be used in a method of forming printed images on surfaces in a heated environment. The method includes projecting a stream of droplets of the ink composition onto a surface to form the desired printed image. The inkjet ink composition may be established on the substrate via any suitable inkjet printing techniques. Non-limitative examples of such inkjet printing techniques include thermal, acoustic, and piezoelectric inkjet printing. In some embodiments, the inks are utilized in thermal inkjet printers. An example of method of prolonging the service life of the inkjet print head includes discharging ink from an orifice onto a media substrate wherein the ink contains an inkjet vehicle, from about 0.1 to about 10 weight percentage of colorants, from about 0.01 to about 10 weight percentage of anti-kogation agents, and from about 0.01 to about 10 weight percentage of dispersed resin beads.

Another example of method of inkjet printing over a prolonged period of time, includes jetting an inkjet ink onto a media substrate, wherein the inkjet ink includes: an inkjet vehicle, from about 0.1 to about 10 weight percentage of colorants, from about 0.01 to about 10 weight percentage of anti-kogation agent having the formula (II) wherein n is from 0 to 15:

and from about 0.01 to about 10 weight percentage of dispersed resin beads including an organic polymer or an inorganic polymer and a functional group selected from the group consisting of iminodiacetic acid group (IDA) or aminomethylphosphonic acid (AMPA) group or diethylenetriaminetetraacetate (TAAcOH) group.

The introduction of a combination of anti-kogation agents and resin beads, such as disclosed herein, reduces the kogation phenomenon of resistors and, in addition, ameliorates or even substantially eliminates clogging phenomenon that can happen in internal ink channels, in firing chambers, or in nozzles of the printhead. Examples of ink compositions extend thus the life of inkjet pens in general (and particularly thermal inkjet pens) which carry such inks.

The images are printed on porous and non-porous surfaces, in some embodiments on porous surfaces, using the ink composition of embodiments of the present disclosure. In other embodiments, the substrate is paper (non-limitative examples of which include plain copy paper or papers having recycled fibers therein) or photo-paper (non-limitative examples of which include polyethylene or polypropylene extruded on one or both sides of paper), and/or combinations thereof. In some embodiments, the substrate has a thickness along substantially the entire length ranging between about 0.025 mm and about 0.5 mm. In some embodiments, the printed surface can be any plastic coated media (as used in out-door signage) and tracing media (for architectural drawings).

As used herein, “images” refers to marks, signs, symbols, figures, indications, and/or appearances deposited upon a substrate with either visible or an invisible ink composition. Examples of an image can include characters, words, numbers, alpha-numeric symbols, punctuation, text, lines, underlines, highlights, and the like.

In other embodiments, the inks are utilized in an inkjet set including, at least, magenta, cyan, yellow and black inks. Colorless ink compositions that contain non-colored particles and no colorant may also be used.

The following examples illustrate the embodiments of the disclosure that are presently best known. However, it is to be understood that the following are only exemplary or illustrative of the application of the principles of the present invention. Numerous modifications and alternative compositions, methods, and systems may be devised by those skilled in the art without departing from the spirit and scope of the present invention. The appended claims are intended to cover such modifications and arrangements. Thus, while the present invention has been described above with particularity, the following examples provide further details in connection with what are presently deemed to be the most practical and preferred embodiments of the invention.

Example 1 Ink Formulations

Ink compositions are prepared in accordance with Table A as follows. All numbers represent the weight percentage of each component by total weight of the ink composition. Ink formulations B, C, D and E are comparative inks.

TABLE A Formulations A B C D E 1-(2 hydroxy- 8.00 8.00 8.00 8.00 8.00 ethyl)- 2-pyrrolidone 2-pyrrolidone 7.00 7.00 7.00 7.00 7.00 1,6-Hexanediol 3.00 3.00 3.00 3.00 3.00 Tetraethylene 3.00 3.00 3.00 3.00 3.00 Glycol Liponic ® EG-1 2.00 2.00 2.00 2.00 2.00 Surfynol ® SEF 1.10 1.10 1.10 1.10 1.10 Crodafos ® N-3 1.00 1.00 1.00 1.00 — Proxel ® GXL 0.10 0.10 0.10 0.10 0.10 Kordek ® MLX 0.14 0.14 0.14 0.14 0.14 Joncryl ® 683 0.20 0.20 0.20 0.20 0.20 (K salt) QuadraPure ® 0.75 — 9.20 — 6.70 IDA Colorant 3.00 3.00 3.00 3.00 3.00 Water Up Up Up Up Up to 100 to 100 to 100 to 100 to 100 Extra Ca²⁺ — —  0.0006   0.00005 —

Surfynol® SEF is a surfactant available from Air Products. Joncryl® 683 is an acrylic resin available from BASF. Proxel® GXL is a Biocide available from Zeneca. Crodafos® N-3 acid is available from Croda Inc. Liponic® EG-1 is a surfactant available from Dow Corning. Kordek® MLX is a biocide available from Rohm and Haas. QuadraPure® IDA are resin beads available from Reaxa Corp.

Example 2 Kogation Performance of Ink Composition

Ink compositions are evaluated for their efficacy in reducing kogation. Inkjet inks formulation A and E are loaded into two different thermal inkjet architectures and fired initially for baseline readings related to steady state drop weight. Each ink composition is printed through its respective print architecture at 400 million drops per nozzle. The nozzle size for this particular study is about 20 microns. The kogation performance is determined by measuring the drop weight retained after significant volume of ink firing. The kogation test is carried out with multiple repeating pens for average results. The drop weight, expressed in nanograms (ng), is determined for the ink compositions A and E at 0, 1, 10, 50, 100, and 200 million drops/nozzle (MDPN). The results are illustrated in FIG. 1.

As shown in FIG. 1, the control composition E shows poor or marginal kogation performances. A significant decrease in the drop weight is observed over the course of firing 10 million drops/nozzle. On the opposite, ink composition A shows good kogation performances.

In addition, after printing, the resistor surfaces are visually inspected with an optical microscope to determine whether kogation is present. 100× optical image of resistor surfaces is determined for the ink compositions A and E after 400 million drops/nozzle. The results are illustrated in FIG. 2. FIG. 2 shows 100× optical images of resistor surfaces for ink compositions A and E after kogation testing on the resistor life tester. FIG. 2 demonstrates that the resistor surface of composition A is cleaner compared to that observed with the ink composition E, i.e., there is no deposit on the surface of the resistor. This means thus that composition E shows poor kogation performances while ink composition A shows a significant improvement in the kogation performances.

Example 3 Calcium Binding Capacities

Compositions are evaluated herein for their capacity in binding metals ions. The efficiency to bind calcium reflects the anti-clogging effect of the ink components.

Compositions including resin beads and different anti-kogation agents (Crodafos® N3, Crodafos® N10 available from Croda Inc.) are stirred with a 20 ppm solution of calcium in deionized water. Anti-kogation agents (Crodafos® N3 or Crodafos® N10) are added to the calcium solution before the addition of resin beads. The samples are stirred at room temperature over the weekend, filtered and submitted for ICP-OES analysis (Inductively coupled plasma—Optical Emission Spectroscopy). The content of calcium present in each solution is then evaluated. The results are summarized in Table B below. The quantity of calcium is expressed in parts per million (ppm) and represents the amount of calcium detected in 20 ppm of solution.

TABLE B Compositions Calcium content 25 g Calcium Solution, 1.6 10 mg QuadraPure ®IDA 25 g Calcium Solution, 1.5 10 mg QuadraPure ®AMPA 25 g Calcium Solution, 20 10 mg PL-MeMal ® 10 g Calcium Solution, 3.2 0.1 g Crodafos ® N3 25 g Calcium Solution, 2.6 0.25 g Crodafos ® N3, 10 mg QuadraPure ®IDA 25 g Calcium Solution, 2.4 0.25 g Crodafos ® N3, 10 mg QuadraPure ®AMPA 10 g Calcium Solution, 20 0.1 g Crodafos ® N10 25 g Calcium Solution, 2.7 0.25 g Crodafos ® N10, 10 mg QuadraPure ®IDA 25 g Calcium Solution, 3.5 0.25 g Crodafos ® N 10, 10 mg QuadraPure ®AMPA Calcium Solution 16 verification limit 1.0

QuadraPure®AMPA is resin bead available from Reaxa. QuadraPure®IDA is resin beads available from Reaxa. PL-MeMal® are resin beads available from the Polymer Labs division of Varian Inc. Crodafos® N3 and Crodafos® N10 are available from Croda Inc.

These results demonstrate that resin beads containing iminodiacetic acid group (IDA) or AMPA aminomethylphosphonic acid group (AMPA) as functional group have good capacity for binding metal ions. These results demonstrate also that some resin beads combined with some anti-kogation agents exhibit good capacity for binding metal ions.

Example 4 Filterability Performances of Ink Compositions

Formulations of Table A are analyzed for their filterability performances. Such filterability performances represent the anti-clogging benefit of the ink compositions, i.e., the ability of not clogging the nozzles and/or the filters of the printhead. The addition of calcium reflects the inclination of anti-kogation agents to precipitate and the tendency of the inks containing them to clog filters and printhead nozzles. The filtration of each ink is evaluated by putting 15 g of each ink through a 1 μm pore size filter. The ink is first spiked with a metal-salt solution (Ca²⁺); the ink is agitated for 2 weeks and is then evaluated. The results are summarized in Table C.

In Table C, the filterability time corresponds to the tendency of ink to clog. The lower the filter time is, the better the anti-clogging effect is. The time taken to filter the given sample is thus an indication of the ink's anti-clogging performance.

TABLE C Ink Ca Resin Time to filter the ink formu- spike beads (in second or in minute) lation (ppm) (grams) Run #1 Run #2 Run #3 B 0 0 13 sec 14 sec 13 sec A 0 0.115 12 sec 13 sec 13 sec D 5 0 5 min/9 mL 5 min/8.5 mL N/A C 60 1.375 12 sec 11 sec 11 sec

As demonstrated herein, the presence of a combination of anti-kogation agents and of resin beads in ink composition clearly reduces the amount of metal (calcium) present in the ink formulation. The results demonstrate that inks containing such combination of anti-kogation agents and of resin beads results in ink compositions that have a low time to filter, meaning thus that such combination does not present clogging effect.

The preceding description has been presented only to illustrate and describe exemplary embodiments of the present invention. Although certain example methods, compositions, apparatus and articles of manufacture have been described herein, the scope of coverage of this patent is not limited thereto. On the contrary, this patent covers all methods, apparatus and articles of manufacture fairly falling within the scope of the claims either literally or under the doctrine of equivalents. 

What is claimed is:
 1. An inkjet ink composition, comprising: a. an inkjet vehicle, b. from about 0.1 to about 10 weight percentage of colorants, c. from about 0.01 to about 10 weight percentage of anti-kogation agents, d. and from about 0.01 to about 10 weight percentage of dispersed resin beads, wherein the resin beads have a diameter that is bigger than a pore size of a filter in an ink delivery system of the inkjet ink composition, and wherein the resin beads are to bind multivalent metal ions.
 2. The inkjet ink according to claim 1 wherein the diameter of the dispersed resin beads is at least 1 μm.
 3. The inkjet ink according to claim 1 wherein the diameter of the dispersed resin beads ranges from about 5 to about 800 μm.
 4. The inkjet ink according to claim 1 wherein the dispersed resin beads comprise an organic polymer or an inorganic polymer and a functional group.
 5. The inkjet ink according to claim 1 wherein the dispersed resin beads contain a functional group selected from the group consisting of iminodiacetic acid group (IDA), aminomethylphosphonic acid (AMPA) group or diethylenetriaminetetraacetate (TAAcOH) group.
 6. The inkjet ink according to claim 1 wherein the anti-kogation agent is a phosphate-containing surfactant.
 7. The inkjet ink according to claim 1 wherein the anti-kogation agent is a phosphate ester surfactant.
 8. The inkjet ink according to claim 1 wherein the anti-kogation agent is a phosphate ester of a fatty alcohol alkoxylate surfactant.
 9. The inkjet ink according to claim 1 wherein the anti-kogation agent is an ethoxylated mono-oleyl phosphate ester surfactant.
 10. The inkjet ink according to claim 1 wherein the anti-kogation agent is selected from the group consisting of oleth-3 phosphate, oleth-10 phosphate, oleth-5 phosphate, dioleyl phosphate, ppg-5-ceteth-10 phosphate, C₉-C₁₅ alkyl monophosphate, deceth-4 phosphate, and mixtures thereof.
 11. The inkjet ink according to claim 1 wherein the anti-kogation agent has the formula (II) and wherein n is from 0 to 15:


12. The inkjet ink of claim 1, wherein the anti-kogation agent is present in an amount representing from about 0.2 to about 3 weight percentage by weight of the ink composition.
 13. The inkjet ink according to claim 1 wherein the colorant is a pigment.
 14. The inkjet ink according to claim 1 wherein the resin beads are selected from the group consisting of a polyamide, an unsaturated a polyester, a polyurethane, an epoxy, a silicone, a copolymer of an unsatured dicarboxylic acid and styrene, a polystyrene cross-linked with divinylbenzene, and precipitated silica, and wherein the resin beads include a functional group selected from the group consisting of a di-acid group, a homologue of ethylenediamine with acetic acid, and a substituted methylphosphonic acid.
 15. A method of inkjet printing over a prolonged period of time, comprising jetting an inkjet ink onto a media substrate, wherein said inkjet ink includes: a. an inkjet vehicle, b. from about 0.1 to about 10 weight percentage of colorants, c. from about 0.01 to about 10 weight percentage of anti-kogation agents, d. and from about 0.01 to about 10 weight percentage of dispersed resin beads, wherein the resin beads have a diameter that is bigger than a pore size of a filter in an ink delivery system of the inkjet ink, and wherein the resin beads are to bind multivalent metal ions.
 16. The method of inkjet printing over a prolonged period of time, according to claim 15, wherein: the anti-kogation agent has the formula (II) and wherein n is from 0 to 15:

and the resin beads include an organic polymer or an inorganic polymer and a functional group selected from the group consisting of iminodiacetic acid group (IDA), aminomethylphosphonic acid (AMPA) group or diethylenetriaminetetraacetate (TAAcOH) group. 